EP1489148B1 - Uv-härtbare beschichtungszusammensetzung sowie beschichtete artikel - Google Patents

Uv-härtbare beschichtungszusammensetzung sowie beschichtete artikel Download PDF

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Publication number
EP1489148B1
EP1489148B1 EP03712798A EP03712798A EP1489148B1 EP 1489148 B1 EP1489148 B1 EP 1489148B1 EP 03712798 A EP03712798 A EP 03712798A EP 03712798 A EP03712798 A EP 03712798A EP 1489148 B1 EP1489148 B1 EP 1489148B1
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EP
European Patent Office
Prior art keywords
meth
component
ingredient
ultraviolet
paint film
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP03712798A
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English (en)
French (fr)
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EP1489148A1 (de
EP1489148A4 (de
Inventor
Takeshi Tsunoda
Shinji Mitsumune
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BASF Japan Ltd
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BASF Japan Ltd
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Priority claimed from JP2002080289A external-priority patent/JP3974434B2/ja
Priority claimed from JP2002318723A external-priority patent/JP4851048B2/ja
Application filed by BASF Japan Ltd filed Critical BASF Japan Ltd
Publication of EP1489148A1 publication Critical patent/EP1489148A1/de
Publication of EP1489148A4 publication Critical patent/EP1489148A4/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/141—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08L61/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/32—Modified amine-aldehyde condensates

Definitions

  • the present invention relates to an ultraviolet-curable coating composition which can be used in the field of aesthetic decoration and has properties suitable for a paint film, for example, scratch resistance, gasoline resistance and gloss-holding property in atmospheric exposure, and a coated article thereof.
  • Japanese patent publication 1960210 and EP-A2-0 247 563 , and JP 1 011 169 and JP 8 311 398 disclose an ultraviolet-curable coating composition comprising an ultraviolet curable polyfunctional (meth)acrylate and acrylic resin, polyisocyanate compound, light stabilizer and photopolymerization initiator.
  • Japanese patent publication 2504061 discloses an ultraviolet-curable coating composition comprising an ultraviolet curable polyfunctional (meth)acrylate and acrylic resin, melamine resin or urea resin, light stabilizer and photopolymerization initiator.
  • the acrylic resin / urethane resin coating compositions and the acrylic resin / melamine resin coating compositions described above are not necessarily sufficient in the distinction of image of the paint film and are insufficient in view of productivity of the paint film because it takes a long time to cure the coating composition.
  • the ultraviolet-curable coating compositions of Japanese patent publication 1960210 and 2504061 give an excellent distinction of image of the paint film and have high level productivity of the paint film, but can not give paint films having excellent scratch resistance.
  • the present invention has an objective to provide an ultraviolet-curable coating composition which can give paint films having scratch resistance and aesthetic decorative properties, as well as excellent adhesion and excellent gasoline resistance, and have high level productivity of the paint film, and coated articles obtained by application of the ultraviolet-curable coating composition.
  • an ultraviolet-curable coating composition comprising a specific ultraviolet curable four or more functional groups-containing polyfunctional (meth)acrylate, a specific lactone-modified polymer of polyhydric alcohol mono(meth)acrylate containing 20 to 60 percents by weight of ⁇ -caprolactone ring-opening addition product and/or a specific lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product, and a non-yellowing polyisocyanate compound and/or an amino resin, in a specific ratio and further, a light stabilizer and a photopolymerization initiator, and the components described above are formulated to obtain a cured paint film having a Knoop hardness of 10 to 18 and a molecular weight of intercrosslinking of crosslinked resin component in the cured paint film of 150 to 300.
  • the present invention provides an ultraviolet-curable coating composition comprising:
  • the present invention provides the ultraviolet-curable coating composition as described above, wherein ingredient (B) is a lactone-modified polymer of polyhydric alcohol mono(meth)acrylate containing 20 to 60 percents by weight of ⁇ -caprolactone ring-opening addition product and having a hydroxyl value derived from the lactone modification of 100 to 180 mgKOH/g.
  • the present invention provides the ultraviolet-curable coating composition as described above, wherein ingredient (B) is a lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product and having a hydroxyl value of 50 to 180 mgKOH/g.
  • the present invention provides the ultraviolet-curable coating composition as described above, wherein ingredient (C) is a non-yellowing polyisocyanate compound and the equivalent value of isocyanate group of ingredient (C) to the hydroxyl group of ingredient (B) is from 0.5 to 1.5.
  • the present invention provides the ultraviolet-curable coating composition as described above, wherein ingredient (C) is an amino resin.
  • the present invention also provides a coated article obtained by applying the ultraviolet-curable coating composition as described above.
  • (meth)acryloyl group means acryloyl group and/or methacryloyl group.
  • (meth)acrylate means acrylate and/or methacrylate and the term, (meth)acrylic acid means acrylic acid and/or methacrylic acid.
  • the ultraviolet curable four or more functional groups-containing polyfunctional (meth)acrylate of ingredient (A), used in the present invention has four or more (meth)acryloyl groups in the molecule.
  • a polyfunctional (meth)acrylate having two (meth)acryloyl groups in the molecule curability is insufficient and gasoline resistance is inferior.
  • a polyfunctional (meth)acrylate having three (meth) acryloyl groups in the molecule is used and a large amount of ingredient (A) is formulated to obtain a cured paint film having a molecular weight of intercrosslinking of crosslinked resin component in the cured paint film of 150 to 300, the increase of curing shrinkage strain in the paint film is caused and adhesive property is inferior.
  • the number average molecular weight of ultraviolet curable four or more functional groups-containing polyfunctional (meth)acrylate of ingredient (A) is from 300 to 2,000, preferably from 320 to 1,500.
  • the number average molecular weight is more than 2,000, leveling property of the paint film is inferior and it is difficult to obtain the high degree of aesthetic decorative property.
  • the number average molecular weight is less than 300, flexibility of the paint film is inferior and crack is easily caused in bending test.
  • the ultraviolet curable four or more functional groups-containing polyfunctional (meth)acrylate of ingredient (A) includes a four or more functional groups-containing polyhydric alcohol (meth)acrylate obtained by esterification of tetravalent or more polyhydric alcohol with (meth)acrylic acid, a four or more functional groups-containing epoxy(meth)acrylate obtained by esterification of epoxy groups of four ormore functional groups-containing polyfunctional epoxy compound with (meth)acrylic acid, a four or more functional groups-containing polyurethane(meth)acrylate obtained by reaction of four or more functional groups-containing polyfunctional isocyanate compound with hydroxyl group-containing (meth)acrylate, and a four or more functional groups-containing melamine(meth)acrylate obtained by reaction of methylolmelanine having four or more methylol groups in a molecule with hydroxyl group-containing (meth)acrylate.
  • the four or more functional groups-containing polyfunctional (meth)acrylate of ingredient (A) can be utilized singly or in
  • the four or more functional groups-containing polyhydric alcohol (meth)acrylate includes pentaerythritol tetra(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, xylitolpenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerildipentaerythritol hepta(meth)acrylate.
  • KAYARAD DPCA-20 KAYARAD DPCA-30
  • KAYARAD DPCA-60 KAYARAD DPCA-120
  • all trade names, products of NIPPON KAYAKU CO. LTD.. are trade names, products of NIPPON KAYAKU CO. LTD..
  • the four or more functional groups-containing polyfunctional epoxy compound used to prepare the four or more functional group-containing epoxy(meth)acrylate includes glycidyl ether epoxy resins such as phenol novolac type glycidyl ether epoxy resins, orthocresol novolac type glycidyl ether epoxy resins, bisphenol A novolac type glycidyl ether epoxy resins, brominated phenol novolac type glycidyl ether epoxy resins and tetraphenylol ethane type glycidyl ether epoxy resins.
  • glycidyl ether epoxy resins such as phenol novolac type glycidyl ether epoxy resins, orthocresol novolac type glycidyl ether epoxy resins, bisphenol A novolac type glycidyl ether epoxy resins, brominated phenol novolac type glycidyl ether epoxy resins and tetraphenylol ethane type
  • the four or more functional groups-containing polyfunctional isocyanate compound used to prepare the four or more functional group-containing polyurethane(meth)acrylate includes reaction products obtained by reaction of hexamethylene diisocyanate and/or isophorone diisocyanate with four or more functional groups-containing polyhydric alcohol such as pentaerythritol and dipentaerythritol.
  • the methylolmelanine having four or more methylol groups in a molecule used to prepare the four or more functional group-containing melamine (meth)acrylate includes tetramethylolmelamine, pentamethylolmelamine and hexamethylolmelamine.
  • the hydroxyl group-containing (meth)acrylate used to prepare the four or more functional group-containing polyurethane(meth)acrylate and the four or more functional group-containing melamine(meth)acrylate includes hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; polyhydric alcohol mono(meth)acrylates such as polyethyleneglycol mono(meth)acrylate, polypropyleneglycol mono (meth) acrylate, neopentylglycol mono(meth)acrylate and glycerin mono(meth)acrylate; ethyleneoxide and/or propyleneoxide addition products of hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-
  • the polyfunctional (meth)acrylate having the acryloyl group in the molecule has high curability compared with the polyfunctional (meth)acrylate having the methacryloyl group in the molecule. Therefore, the polyfunctional (meth)acrylate having the acryloyl group in the molecule is more preferably used in the present invention.
  • Ingredient (A) can be utilized singly or in combination of two or more members.
  • Ingredient (B) used in the present invention is a lactone-modified polymer of polyhydric alcohol mono(meth)acrylate containing 20 to 60 percents by weight of ⁇ -caprolactone ring-opening addition product and having a hydroxyl value derived from the lactone modification of 100 to 180 mgKOH/g (hereinafter, it may be called “ingredient (Ba)”), and/or a lactone-modified polyester resin containing 10 to 50 percents by weight of lactone ring-opening addition product and having a hydroxyl value of 50 to 180 mgKOH/g (hereinafter, it may be called “ingredient (Bb)”),
  • the content of ⁇ -caprolactone ring-opening addition product in ingredient (Ba) is 20 to 60 percents by weight, preferably 25 to 50 percents by weight.
  • the scratch resistance of the paint film is not sufficient.
  • the content of ⁇ -caprolactone ring-opening addition product is more than 60 percents by weight, hardness of the paint film is too low and the gasoline resistance of the paint film is inferior.
  • the hydroxyl value derived from the lactone modification of ingredient (Ba) is 100 to 180 mgKOH/g, preferably 120 to 170 mgKOH/g.
  • the term, "the hydroxyl value derived from the lactone modification” means the hydroxyl value of the hydroxyl group which exist in the end of the structure portion consisting of the ⁇ -caprolactone ring-opening addition product in the lactone-modified polymer of polyhydric alcohol mono(meth)acrylate and does not contain the hydroxyl value of the hydroxyl group in the other structure portion.
  • the hydroxyl value derived from the lactone modification is less than 100 mgKOH/g, the scratch resistance of the paint film is not sufficient.
  • the hydroxyl value derived from the lactone modification is more than 180 mgKOH/g, the compatibility with the four or more functional groups-containing polyfunctional (meth)acrylate of ingredient (A) is inferior.
  • the molecular weight of ingredient (Ba) is not limited particularly.
  • the number average molecular weight of ingredient (Ba) is preferably 2,000 to 20,000 in general.
  • the lactone-modified polymer of polyhydric alcohol mono(meth)acrylate of ingredient (Ba) can be utilized singly or in combination of two or more members.
  • the method for preparing ingredient (Ba) includes (1) a preparation method comprising homopolymerizing polycaprolactone-modified polyhydric alcohol mono(meth)acrylate obtained by ring-opening addition of ⁇ -caprolactone to the polyhydric alcohol mono(meth)acrylate or copolymerizing it and other copolymerizable vinyl monomer, and (2) a preparation method comprising ring-opening adding ⁇ -caprolactone to a homopolymer or a copolymer of polyhydric alcohol mono (meth) acrylate which is obtained by homopolymerizing polyhydric alcohol mono(meth)acrylate or copolymerizing it and other copolymerizable vinyl monomer.
  • the polyhydric alcohol mono(meth)acrylate used in the methods (1) and (2) as described above includes 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, polyethyleneglycol mono(meth)acrylate, polypropyleneglycol mono(meth)acrylate, neopentylglycol mono(meth)acrylate and glycerin mono(meth)acrylate.
  • the polyhydric alcohol mono(meth)acrylate can be utilized singly or in combination of two or more members.
  • the polycaprolactone-modified polyhydric alcohol mono(meth)acrylate used in the method (1) as described above includes polycaprolactone-modified hydroxyalkyl mono(meth)acrylate and polycaprolactone-modified poly(oxyalkylene) mono(meth)acrylate.
  • PLACCEL FA-1 (trade name, produced by Daicel Chemical Industries, LTD. , monomer obtained by ring-opening addition of one mole of ⁇ -caprolactone to one mole of 2-hydroxyethyl acrylate)
  • PLACCEL FM-1D PLACCEL FM-2D
  • PLACCEL FM-3 PLACCEL FM-4
  • PLACCEL FM-4 all trade names, produced by Daicel Chemical Industries, LTD. , monomer obtained by ring-opening addition of one mole, two moles, three moles or four moles of ⁇ -caprolactone respectively to one mole of 2-hydroxyethyl methacrylate.
  • the other copolymerizable vinyl monomers used in the methods (1) and (2) as described above include, for example, (meth)acrylic acid and alkyl substitution products thereof; alkyl(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate and stearyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 3-hydroxypropyl (meth)acrylate; esters of dibasic acid such as itaconic acid, maleic acid and fumalic acid; styrene and nuclear-substituted styrenes such as vinyl toluene, dimethyl styrene and ethyl styrene; and (meth)acrylonitrile, (meth)acrylamide, vinyl acetate and
  • a polymerization initiator in the polymerization for preparation of ingredient (Ba), can be utilized.
  • the polymerization initiator includes organic peroxide polymerization initiators and azo polymerization initiators.
  • the amount of the polymerization initiator is not limited particularly, but preferably 0.5 to 15 percents by weight to total amount of the monomers, in general.
  • Ingredient (Ba) can be utilized singly or in combination of two or more members.
  • the content of lactone ring-opening addition product in ingredient (Bb) is 10 to 50 percents by weight, preferably 15 to 40 percents by weight. When the content of lactone ring-opening addition product is less than 10 percents by weight, the scratch resistance of the paint film is not sufficient. When the content of lactone ring-opening addition product is more than 50 percents by weight, hardness of the paint film is too low and the gasoline resistance of the paint film is inferior.
  • the hydroxyl value of ingredient (Bb) is 50 to 180 mgKOH/g, preferably 70 to 170 mgKOH/g. When the hydroxyl value is less than 50 mgKOH/g, the scratch resistance of the paint film is not sufficient. When the hydroxyl value is more than 180 mgKOH/g, the compatibility with the four or more functional groups-containing polyfunctional (meth)acrylate of ingredient (A) is inferior.
  • the molecular weight of ingredient (Bb) is not limited particularly.
  • the number average molecular weight of ingredient (Bb) is preferably 1,500 to 20,000, more preferably 1,500 to 5,000 in general.
  • the method for preparing ingredient (Bb) includes a preparation method comprising ring-opening addition of a lactone to a polyester resin obtained by bonding a polybasic acid and a polyhydric alcohol.
  • the polybasic acid used in the method described above includes, for example, aromatic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, tetrachloro phthalic acid, naphthalene dicarboxylic acid, 4,4-diphenylmethane carboxylic acid; alicyclic polybasic acids such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, hexahydrotrimellitic acid and methyl hexahydroterephthalic acid; saturated and unsaturated aliphatic polybasic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebasic acid, dodecane dicarboxylic acid, pimelic acid, maleic acid, fumaric acid and itaconic acid.
  • aromatic polybasic acids such as phthalic acid, iso
  • anhydrides of the polybasic acids described above and ester-formable substitution product thereof for example, ester of lower alkyl having 1 to 6 carbon atoms, can be utlized as the polybasic acid.
  • the polybasic acid can be utilized singly or in combination of two or more members.
  • polyhydric alcohol described above examples are divalent alcohols and trivalent or more alcohols described below.
  • the divalent alcohols include, for example, glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyl trimethylene glycol, tetramethylene glycol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, 1,4-cyclohexane dimethanol and neopentyl glycol; polyether diols such as alkylene oxide addition products of bisphenol A
  • trivalent or more alcohols include, for example, glycerin, trimethylol ethane, trimethylol propane, diglycerin, pentaerythritol, dipentaerythritol and sorbitol.
  • compounds having two or more epoxy groups in the molecule like bisphenol A diglycidyl ether can be utilized as the trivalent or more alcohol.
  • the polyhydric alcohol can be utilized singly or in combination of two or more members.
  • saturated aliphatic fatty acids such as octyl acid, lauryl acid and stearic acid
  • unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and eleostearic acid
  • monobasic acids such as benzoic acid, abietic acid, acetic acid, propionic acid and butyricacid
  • hydroxycarboxylic acid compounds such as methylol propionic acid, pivalic acid, 12-hydroxystearic acid and ricinolic acid
  • oils and fats such as linseed oil, castor oil, tall oil, cotton seed oil, soybean oil, olive oil and safflower oil can be utilized as other components according to needs, other than the components described above and before.
  • the components described above can be utilized singly or in combination of two or more members.
  • Lactones used for preparing ingredient (Bb) of the present invention include ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone, y -valerolactone, y -caprolactone, y -nonanoic lactone and ⁇ -dodecanolactone.
  • ⁇ -caprolactone is preferably used.
  • the lactone can be utilized singly or in combination of two or more members.
  • Ingredient (Bb) can be utilized singly or in combination of two or more members.
  • Ingredient (C) used in the present invention is a non-yellowing polyisocyanate compound and/or an amino resin.
  • non-yellowing polyisocyanate compound aliphatic and alicyclic polyisocyanate compounds are preferably used. Typical examples are reaction products of hexamethylene diisocyanate and/or isophorone diisocyanate with polyhydric alcohol and/or low molecular weight polyester polyol, isocyanurate compounds such as polymer of hexamethylene diisocyanate and/or isophorone diisocyanate and biuret compounds obtained by further reaction to the urethane bond. Also, blocked isocyanates in which the isocyanate groups in the polymers are masked with hydroxyl group-containing compounds, can be preferably utilized. Further, various non-yellowing polyisocyanate compounds such as polymers of diisocyanate compounds other than the compounds described above can be utilized. The non-yellowing polyisocyanate compound can be utilized singly or in combination of two or more members.
  • the amino resin melamine resins or urea resins used generally for coating compositions can be utilized.
  • the resins include melamine resins or urea resins which are etherificated with lower alcohol such as methanol, n-butanol and isobutanol singly or in mixture thereof.
  • the amino resin can be utilized singly or in combination two or more members.
  • non-yellowing polyisocyanate compound and the amino resin can be used in combination.
  • the weight ratio of ingredient (A) to the total weight of ingredient (B) and ingredient (C) is 10:90 to 50:50, preferably 15:85 to 45:55, more preferably 20:80 to 40:60, and the weight ratio of ingredient (B) to ingredient (C) is 90:10 to 20:80, preferably 80:20 to 30:70.
  • the equivalent value of the isocyanate group in ingredient (C) to one equivalent of hydroxyl group in ingredient (B) is preferably 0.5 to 1.5 equivalent, more preferably 0.6 to 1.2 equivalent.
  • the light stabilizer of ingredient (D) used in the present invention is used for increasing weathering resistance of the paint film.
  • the light stabilizer includes compounds which are dissolved or dispersed homogeneously in the paint film, does not cause curing inhibition at the time of ultraviolet-curable, and does not cause yellowing of the paint film.
  • the light stabilizer includes ultraviolet absorbents and antioxidants.
  • the ultraviolet absorbents include, for example, benzophenone or derivatives thereof, phenylsalicylate or derivatives thereof, benzotriazole or derivatives thereof, and cyanoacrylate or derivatives thereof. Among them, benzotriazole based ultraviolet absorbents are preferable particularly.
  • the antioxidants include phenol based antioxidants, organic phosphite based antioxidants, organic thioether based antioxidants and hindered amine based antioxidants. In particular, the hindered amine based antioxidants are preferable.
  • the light stabilizer can be utilized singly or in combination of two or more members.
  • the amount of the light stabilizer is preferably 0.5 to 5 parts by weight to 100 parts by weight of the total amount of ingredient (A), ingredient (B) and ingredient (C).
  • Photopolymerization initiator of ingredient (E) used in the present invention includes benzoin or derivatives thereof, benzophenone or derivatives thereof, acetophenone or derivatives thereof, Michler's ketone, benzyl or derivatives thereof, tetraalkyl chiuram monosulfide and thioxane, having absorption in ultraviolet area of 260 to 450 nm. Among them, acetophenone or derivatives thereof are preferable particularly.
  • the photopolymerization initiator can be utilized singly or in combination of two or more members.
  • the amount of the photopolymerization initiator is preferably 0.5 to 5 parts by weight to 100 parts by weight of the total amount of ingredient (A), ingredient (B) and ingredient (C).
  • the ultraviolet-curable coating composition of the present invention can be further formulated properly with one or not less than two members of dilution solvents for controlling viscosity, sensitizers of photopolymerization reaction such as amine compounds, urea compounds and sulfur compounds which are used generally for ultraviolet-curable coating composition, organic peroxides for proceeding the polymerization curing homogeneously, pigments, dyes.
  • the components described before are formulated to be able to obtain a cured paint film having a Knoop hardness of 10 to 18, preferably 11 to 18 and a molecular weight of intercrosslinking of crosslinked resin component in the cured paint film of 150 to 300, preferably 170 to 280.
  • Knoop hardness of the cured paint film is less than 10, gasoline resistance is inferior.
  • Knoop hardness of the cured paint film is more than 18, scratch resistance is inferior.
  • the graphic tape is generally a graphic tape formed by providing such as printing and applying, of a display such as literatures of maker name, product name and the like, symbols, marks, figures and patterns on the surface of the substrate being a sheet of resin such as vinyl chloride resins and urethane resins, by applying a clear coating composition such as urethane resin clear coating composition on the surface of the display, by drying, and then by pattern-draw-molding.
  • the graphic tape includes graphic tapes formed by providing a display of metal vapor deposition such as aluminum vapor deposition and chromium vapor deposition on the surface of a sheet of resin such as polyethylene terephthalate resin.
  • Knoop hardness is a hardness of the paint film measured at 20 °C by micro surface hardness meter ( produced by Shimazu Co., trade name "HMV-2000" ). As the value of Knoop hardness increases, the paint film becomes harder.
  • Mc is the molecular weight of intercrosslinking of crosslinked resin component ( g/mol )
  • ⁇ is a density of the paint film ( g/cm 3 )
  • G' is a dynamic rigidity in rubber area (E'/3(dyne/cm 2 )) and E' is a dynamic modulus of elasticity in rubber area (dyne/cm 2 ).
  • the method of applying the ultraviolet-curable coating composition of the present invention is not limited particularly.
  • the cured paint film can be obtained by applying the ultraviolet-curable coating composition on the coated article described above by methods such as spraying application, electrostatic application and curtain flow application, and irradiating ultraviolet light to cure.
  • spraying application electrostatic application and curtain flow application
  • irradiating ultraviolet light to cure before the ultraviolet light is irradiated, preheating for removing solvents can be provided, or after the ultraviolet light is irradiated, afterheating can be provided.
  • the temperature of preheating is not limited, but is preferably not less than 50 °C for increasing volatility of solvent.
  • the temperature of afterheating is preferably not less than 80 °C for promoting curing of amino resin.
  • the upper limit of temperature of the preheating or afterheating is not limited, but is preferably not more than 200 °C.
  • the irradiation of ultraviolet light is conducted preferably by using an ultraviolet irradiation device, which can irradiate to the surface of three-dimensional coated article almost homogeneously.
  • an ultraviolet irradiation device which can irradiate to the surface of three-dimensional coated article almost homogeneously.
  • ultraviolet light sources high-pressure mercury lamps, metal halide lamps can be used.
  • the condition of ultraviolet light irradiation for curing the coated article includes a method of irradiating for long time with weak ultraviolet light and a method of irradiating for short time with strong ultraviolet light. Any one of the methods can be selected arbitrarily. When the weak ultraviolet light is irradiated for short time, the amount of ultraviolet energy for giving to the coated film runs short and therefore the curing is defective.
  • the amount of ultraviolet energy for giving to the coated film is excess and therefore the paint film causes yellowing discoloration.
  • Preferable amount of ultraviolet energy for curing the coated article is 100 to 5000 mJ/cm 2 .
  • the thickness of the paint film obtained by applying the ultraviolet-curable coating composition of the present invention can be selected properly according to needs, but is preferably 10 to 200 ⁇ m of the dried thickness, in general.
  • Coated articles obtained by applying the ultraviolet-curable coating composition of the present invention is not particularly limited, but include structures, wood articles, metallic articles, plastics articles, rubber articles, coated papers, ceramic articles and glass articles, specifically automobiles, parts for automobiles (for example, body, bumper, spoiler, mirror, wheel and inner package material, and these parts are made of various materials), metal plates such as steel plates, two-wheel vehicles, parts for two-wheel vehicles, materials for road (for example, guard rail, traffic control sign and sound-proof wall), materials for tunnel (for example, side wall plate), marine vessels, railway vehicles, airplanes, furnitures, musical instruments, house-hold electric instruments, building materials, vessels, office articles, sport articles and toys.
  • parts for automobiles for example, body, bumper, spoiler, mirror, wheel and inner package material, and these parts are made of various materials
  • metal plates such as steel plates, two-wheel vehicles, parts for two-wheel vehicles, materials for road (for example, guard rail, traffic control sign and sound-proof wall), materials for tunnel (for example, side wall plate), marine vessels, railway
  • a skin was rubbed by reciprocating 1000 times under a load of 1 kg by using a RUBBING TESTER (produced by OHIRA RIKA Industry Co., Ltd.).
  • the scratch trace was observed by visual and the evaluation was conducted according to the following standard.
  • the distinction of image of the cured film was measured by a portable distinction of image and gloss meter PGD-IV produced by TOKYO KODEN Co., Ltd. When the value is not less than 0.9, the distinction of image is good.
  • the cutting lines were marked on the paint film by a cutting knife as the cut reached to the substrate under the paint film and 100 of cross-hathced square (1mm ⁇ 1mm) were depicted.
  • a pressure sensitive adhesive cellophane tape was adhered on the surf ace of the paint film, and then peeled rapidly from the surface of the paint film. The condition of the peeled surface of the paint film was observed and the adhesion was evaluated according to the following Standard.
  • test piece was immersed in regular gasoline (produced by NIPPON OIL CORPORATION.) at 20 °C for 24 hours. The appearance of the test piece was observed by visual. The gasoline resistance was evaluated according to the following standard.
  • the part of the paint film on which a graphic tape ( produced by SUMITOMO 3M Co. ) was adhered, was observed by visual.
  • the resistance against to graphic tape test was evaluated according to the following standard.
  • the ultraviolet-curable coating compositions were prepared by mixing homogeneously all components of components (A) to (E) and SOLVESSO 100 indicated in Tables 1 to 4 in the ratio of the formulation amount indicated in Tables 1 to 4.
  • Acrylic resin / melamine resin based white coat solid coating composition (trade name "BELCOAT HS-1 WHITE", a product of BASF NOF Coatings Co., Ltd.) was applied by spraying to a PB-137 treated dull steel plate ( 70 mm in length, 150 mm in width and 0.8 mm in thickness) in an amount to form a film having dried thickness of 40 ⁇ m. After leaving the coated steel plate at room temperature for 10 minutes, the coated steel plate was baked at 140 °C for 30 minutes.
  • a graphic tape ( produced by SUMITOMO 3M Co.
  • the ultraviolet-curable coating compositions of Examples 1 to 13 were applied by spraying to coated steel plate adhered with the graphic tape or without the graphic tape in an amount to form a film having dried thickness of 60 ⁇ m.
  • the coated steel plate was left at room temperature for 2 minutes. And then, the coated steel plate was heated for 3 minutes to reach the temperature of 70 °C by a far infrared heater ( produced by NIHON GAISHI Co.
  • Example 1 Example 2
  • Example 3 Component(A) A1 (*1) 10.0 15.0 20.0 A2 (*2) - - - A3 (*3) - - - Component(B) B1 (*4) 48.9 42.8 - B2 (*5) - - - B3 (*6) - - - B4 (*7) - - 36.7 B5 (*8) - - - Component(C) C1 (*14) 20.7 18.1 15.5 Component(D) D1 (*17) 0.5 0.5 0.5 D2 (*18) 0.5 0.5 0.5 0.5 Component(E) E1 (*19) 0.5 0.5 0.5 0.5 SOLVESSO 100 (*20) 18.9 22.6 26.3 Total 100.0 100.0 100.0 100.0 Component(A)/Components (B) and (C) (weight ratio of nonvolatile matter) 20/80 30/70 40/60 Component (B)/Component (C) (weight ratio of nonvolatile matter)
  • the ultraviolet-curable coating compositions were prepared by mixing homogeneously all components of components (A) to (E) and SOLVESSO 100 indicated in Tables 5 to 11 in the ratio of the formulation amount indicated in Tables 5 to 11.
  • test pieces were prepared in the same method as described in Example 1 except that each of the coating composition of Comparative Examples 1 to 30 was used instead of the ultraviolet-curable coating composition of Example 1.
  • the properties of the obtained test pieces are shown in the low portion of Tables 5 to 11.
  • the ultraviolet-curable coating composition of the present invention can form the cured paint film having excellent scratch resistance and high degree of aesthetic decorative property, also excellent adhesion and gasoline resistance, and has high productivity of paint film.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Polymers & Plastics (AREA)
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Claims (6)

  1. Ein ultravioletthärtende Beschichtungszusammensetzung, umfassend:
    (A) ein ultravioletthärtendes, vier oder mehr funktionelle Gruppen enthaltendes polyfunktionelles (Meth)acrylat mit vier oder mehr (Meth)acryloyl-Gruppen im Molekül und einem zahlengemittelten Molekulargewicht von 300 bis 2000,
    (B) ein Lacton-modifiziertes Polymer eines mehrwertigen-Alkohol-Mono(meth)acrylats, welches 20 bis 60 Gewichtsprozent eines ε-Caprolacton-Ringöffnungs-Additionsprodukts enthält und eine aus der Lacton-Modification abgeleiteten Hydroxylzahl von 100 bis 180 mg KOH/g aufweist, und/oder ein Lacton-modifiziertes Polyesterharz, welches 10 bis 50 Gewichtsprozent eines Lacton- Ringöffnungs-Additionsprodukts enthält und eine Hydroxylzahl von 50 bis 180 mg KOH/g aufweist,
    (C) eine nicht-vergilbende Polyisocyanat-Verbindung und/oder ein Aminoharz,
    (D) einen Lichtstabilisator, und
    (E) einen Photopolymerisationsinitiator,
    worin das Gewichtsverhältnis von Komponente (A) zum Gesamtgewicht der Komponenten (B) und (C) 10 : 90 bis 50 : 50 ist, das Gewichtsverhältnis von Komponente (B) zur Komponente (C) 90 : 10 bis 20 : 80 ist und die oben beschriebenen Komponenten formuliert sind, um einen gehärteten Lackfilm mit einer Knoop-Härte von 10 bis 18 und einem Vernetzungs-Molekulargewicht der vernetzten Harzkomponenten im gehärteten Lackfilm von 150 bis 300 zu erhalten,
    wobei die Knoop-Härte die Härte des Lackfilms ist, welche bei 20°C mit einem Mikro-Härteprüfgerät HMV-2000® der Firma Shimazu Co. gemessen wurde,
    und
    das Vernetzungs-Molekulargewicht der vernetzten Harzkomponenten ein Wert ist, der aus dem dynamischen Steiflgkeitsmodul im Gummi-Bereich des getrennten Lackfilms erhalten wird, welcher bei einer Frequenz von 110Hz und einer Temperatur-Steigerungsrate von 2°C pro Minute unter Verwendung einer erzwungener-Streckschwingungstyp-Viskoelastizität-Messvorrichtung (REHOVIBRON DDV-II-EA®, hergestellt durch Toyo Baldwin Co.) gemessen wird und durch folgende Formel dargestellt wird: Mc = 293 × ρ / log 10 ⁢ Gʹ - 7 ,
    Figure imgb0003
    worin Mc das Vernetzungs-Molekulargewicht der vernetzten Harzkomponenten ist (g/mol), p die Dichte des Lackfilms Ist (g/cm3), G' die dynamische Steifheit im Gummi-Bereich ist (E'/3 (Dyn/cm2)) und E' das dynamische Elastizitätsmodul im Gummibereich ist (Dyn/cm2).
  2. Die ultravioletthärtende Beschichtungszusammensetzung nach Anspruch 1, worin die Komponente (B) ein Lacton-modifiziertes Polymer eines mehrwertigen-Alkohol-Mono(meth)acrylats ist, welches 20 bis 60 Gewichtsprozent eines ε-Caprolacton-Ringöffnungs-Additionsprodukts enthält und eine aus der Lacton-Modifikation abgeleiteten Hydroxylzahl von 100 bis 180 mg KOH /g aufweist.
  3. Die ultravioletthärtende Beschichtungszusammensetzung nach Anspruch 1, worin die Komponente (B) ein Lacton-modifiziertes Polyesterharz ist, welches 10 bis 50 Gewichtsprozent eines Lacton-Ringöffnungs-Additionsprodukts enthält und eine Hydroxylzahl von 50 bis 180 mg KOH/g aufweist.
  4. Die ultravioletthärtende Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 3, worin Komponente (C) eine nicht-vergilbende Polyisocyanat-Verbindung ist und der Äquivalenzwert der IsocyanatGruppen der Komponente (C) zu den Hydroxyl-Gruppen der Komponente (b) von 0,5 bis 1,5 ist.
  5. Die ultravioletthärtende Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 3, worin Komponente (C) ein Aminoharz ist.
  6. Ein beschichteter Körper, der durch das Auftragen der ultrovioletthörtenden Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 5 erhalten wird.
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CN104003877B (zh) * 2014-04-25 2016-01-20 江苏利田科技股份有限公司 一种8官能度脂肪族环氧丙烯酸酯及其制备方法与应用
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